Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

As a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia - Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O(3), NO, NO(2), CO, VOC, CO(2), and H(2)O. Aerosol loads were characterized by concentrations of total aerosol number (CN) and cloud condensation nuclei (CCN), and by light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios within the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h(-1). Within the plume core, aerosol concentrations were strongly enhanced, with Delta CN/Delta CO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. Delta CN/Delta CO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large fraction of the total particle number served as CCN (about 60-80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16 +/- 12 %) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The CO-normalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species. We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NO(x) and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NO(x)) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NO(x). The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NO(x) control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NO(x) emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m(-2) s(-1) close to Manaus, and decreased only to about 2 nmol m(-2) s(-1) within a travel distance >1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was similar to 70 kg N ha(-1) a(-1) decreasing only to about 30 kg N ha(-1) a(-1) after three days of simulation.

Collision probabilities in the rarefaction fan of asymmetric exclusion processes

We consider the one-dimensional asymmetric simple exclusion process (ASEP) in which particles jump to the right at rate p is an element of (1/2, 1.] and to the left at rate 1 - p, interacting by exclusion. In the initial state there is a finite region such that to the left of this region all sites are occupied and to the right of it all sites are empty. Under this initial state, the hydrodynamical limit of the process converges to the rarefaction fan of the associated Burgers equation. In particular suppose that the initial state has first-class particles to the left of the origin, second-class particles at sites 0 and I, and holes to the right of site I. We show that the probability that the two second-class particles eventually collide is (1 + p)/(3p), where a collision occurs when one of the particles attempts to jump over the other. This also corresponds to the probability that two ASEP processes. started from appropriate initial states and coupled using the so-called ""basic coupling,"" eventually reach the same state. We give various other results about the behaviour of second-class particles in the ASEP. In the totally asymmetric case (p = 1) we explain a further representation in terms of a multi-type particle system, and also use the collision result to derive the probability of coexistence of both clusters in a two-type version of the corner growth model.

From demagnetizing to magnetizing interactions in CoFe-AgCu granular films

CoFe-AgCu granular films of compositions ranging from 0.17-0.44 ferromagnetic atomic concentration were prepared by rf sputtering. The microstructure and the transport and magnetic properties suggested that this family of samples can be classified into two groups with a crossover concentration at about 32 at. %. The experimental results for samples Co34Fe8Ag54Cu4 and Co18Fe8Ag70Cu4, which are representative of both different behaviors, are discussed. For the as-prepared sample with higher CoFe content, an uncompensated out-of-plane antiferromagneticlike microstructure with dominant demagnetizing interactions was observed. The particle growth through the annealing led to large in-plane ferromagneticlike clusters with dominant magnetizing interactions. The thermal dependence of the remanence-to-saturation ratio of the as-prepared and annealed samples indicated the existence of a high degree of magnetic correlations leading to a very low magnetoresistivity: In none of the cases was a Stoner¿Wohlfarth behavior observed. On the contrary, for the sample with lower CoFe content, the magnetoresistivity change was much higher, and the remanence followed the expected behavior, since magnetic correlations were strongly reduced through dilution.

Dióxido de estanho nanoestruturado: síntese e crescimento de nanocristais e nanofitas

The objectives of this work are to supply a basic background on nanostructured materials and also to report about the obtaining of nanoparticles, mainly, tin dioxide nanocrystalline particles (obtained by using the polymeric precursor method) presenting a high stability against particle growth due to the usage of a metastable solid solution. The synthesis and growth of SnO2 nanoribbons by a carbothermal reduction process are also discussed.

Testing the influence of small crystals on ice size spectra using Doppler lidar observations

Analysis of the vertical velocity of ice crystals observed with a 1.5micron Doppler lidar from a continuous sample of stratiform ice clouds over 17 months show that the distribution of Doppler velocity varies strongly with temperature, with mean velocities of 0.2m/s at -40C, increasing to 0.6m/s at -10C due to particle growth and broadening of the size spectrum. We examine the likely influence of crystals smaller than 60microns by forward modelling their effect on the area-weighted fall speed, and comparing the results to the lidar observations. The comparison strongly suggests that the concentration of small crystals in most clouds is much lower than measured in-situ by some cloud droplet probes. We argue that the discrepancy is likely due to shattering of large crystals on the probe inlet, and that numerous small particles should not be included in numerical weather and climate model parameterizations.

Photoluminescence of Eu(3+) ion in SnO(2) obtained by sol-gel

Photoluminescence data of Eu-doped SnO(2) xerogels are presented, yielding information on the symmetry of Eu(3+) luminescent centers, which can be related to their location in the matrix: at lattice sites, substituting to Sn(4+), or segregated at particles surface. Influence of doping concentration and/or particle size on the photoluminescence spectra obtained by energy transfer from the matrix to Eu(3+) sites is investigated. Results show that a better efficiency in the energy transfer processes is obtained for high symmetry Eu(3+) sites and low doping levels. Emission intensity from (5)D(0) -> (7)F(1) transition increases as the temperature is raised from 10 to 240 K, under excitation at 266 nm laser line, because in this transition the multiphonon emission becomes significant only above 240 K. As an extension of this result, we predict high effectiveness for room temperature operation of Eu-based optical communication devices. X-ray diffraction data show that the impurity excess inhibits particle growth, which may influence the asymmetry ratio of luminescence spectra.

Silver nanoparticles synthesized by thermal reduction of a silver(I)-aspartame complex in inert atmosphere

Synthesis of silver nanoparticles by thermal treatment of a silver-aspartarne complex under inert atmosphere is described. Spherical metallic silver naroparticles with average diameter of 5 +/-2 nm were obtained by thermal treatment of the complex [Ag(C14H17N2O5)] 1/2H(2)O at 185 degrees C. Thermogravimetric and infrared analysis of the product show the occurrence of an ester bond cleavage of the aspartame ligand followed by rearrangement and release of a molecule of formaldehyde (H2CO), which is transformed in two strong reducing molecules, H-2 and CO. For silver reduction, the presence of the formaldehyde molecules seems to be the key process for the metallic nanoparticles fort-nation. The maintenance of the ligand crystalline structure, with the exception of the ester group loss, was noted as essential for nanoparticles formation and size control. The ligand crystalline structure was completely lost at 200 degrees C and particle growth and coalescence were observed above 250 degrees C. (C) 2005 Elsevier B.V. All rights reserved.

Alloys and oxides on carbon-supported Pt-Sn electrocatalysts for ethanol oxidation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The effect of EU3+ ion doping concentration in Gd2O3 fine spherical particles

This work reports on the preparation of Gd2O3, cubic system, with spherical particles, narrow size distribution, whether or not doped with 1-5 at.% of Eu3+ and the influence of Eu3+ concentration on optical and morphological properties. Average diameter and size distribution particle analyses were performed for all samples from SEM results. Doped samples were also investigated by luminescence spectroscopy and emission kinetic measurements. All oxide samples present a particle average diameter distribution range from 110 to 150 nm and a decrease of particle average diameter with the presence of Eu3+. The particle size decrease is almost the same for all samples with different doping ion concentration. Therefore, the presence of doping ion may be inhibiting particle growth after the nucleation process. From spectroscopic studies, the doping ion distribution in the surface of oxide samples can be considered homogeneous because concentration quenching is not observed, as well as a significant difference among the calculated lifetime for each sample. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Microstructural and morphological analysis of pure and Ce-doped tin dioxide nanoparticles

Structural morphological studies in pure and Ce-doped tin dioxide nanoparticles with high stability against particle growth were performed in samples, obtained using the polymeric precursor method and prepared at different annealing temperatures. A Ce-rich surface layer was used to control the particle size and stabilize SnO2 against particle growth. The formation of this segregated layer can contribute to a decreased surface energy, acting in the driving force, or reducing the surface mobility. Only the cassiterite SnO2 phase was observed below 1000 degreesC and a secondary phase (CeO2) was observed for the Ce-doped SnO2 at temperatures higher than 1000 degreesC, when de-mixing process occurs. The evolution of crystallite size, microstrain and morphology of the nanoparticles with annealing temperatures was investigated by X-ray diffraction (XRD), associated to Rietveld refinements, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Development of metal oxide nanoparticles by soft chemical method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

EPR of Mn as densifying agent in SnO2 powders

Electron Paramagnetic Resonance (EPR) spectra have been obtained at room temperature and at X-band in powders of SnO2 doped with Mn from 0.3 to 10% and submitted to heat treatment from 500 to 900 °C. Mn ions are probably located at particle surfaces as Mn2+, evidenced by its single EPR line which narrows by the exchange interaction effect due to particle growth observed by the BET technique. In samples doped above 1% formation Of Mn3O4 is detected on particle surfaces and a small quantity of Mn is thermally diffused into the bulk as Mn4+. Powders compacted and sintered at 1300 °C confirmed that Mn2+ ions remain at grain boundaries acting as densifying agent.

Estudio de PMN cerámico dopado con KNbO3 y LiNbO 3 sintetizado por Pechini

PMN belongs to a special class of materials named relaxor ferroelectrics. It has high volumetric efficiency due to its high dielectric constant, which makes it in a perfect material for application in multilayer capacitors. When prepared the columbite route its preparation has many advantages. In this work, the preparations of columbite and PMN were done by Pechini and Partial Oxalate methods, respectively. The effects of the KNbO3 and LiNbO3 dopants added in various concentrations. The idea is founded on the correlations that they have with BaTiO3 y PbTiO3, respectively. The whole process was supervised by TG/DTA, XRD, SEM and determination of the specific surface area of the powders. LiNbO3 carries out the pre-sinterization of the particles, observed by a reduction in the surface area. There are not particle grow, but occur its lengthening. However, for KNbO3 these particle growth, but the agglomerates are softer. The effect produced by the doping during the synthesis of the PMN powder is different from the one produced in the columbite precursor. Pure precursor shows an average particle size of 0,2μm, but the addition of 5,0mol% of dopants carries out the formation of agglomerates close to 4μm. LiNbO 3 addition carries out spherical particles and pre-sinterization, while KNbO3 addition does not change the particles shape.

An analysis of diurnal cycles in the mass of ambient aerosols derived from biomass burning and agro-industry

Strong diurnal cycles in ambient aerosol mass were observed in a rural region of Southeast Brazil where the trace composition of the lower troposphere is governed mainly by emissions from agro-industry. An optical particle counter was used to record size-segregated aerosol number concentrations between 13 May 2010 and 15 March 2011. The data were collected every 10 min and used to calculate aerosol mass concentrations. Aerosol samples were also collected onto filters during daytime (10:00-16:00 local time) and nighttime (20:00-06:00) periods, for subsequent analysis of soluble ions and water-soluble organic carbon. Biomass burning aerosols predominated during the dry winter, while secondary aerosols were most important in the summer rainy season. In both seasons, diurnal cycles in calculated aerosol mass concentrations were due to the uptake of water by the aerosols and, to a lesser extent, to emissions and secondary aerosol formation. In neither season could the observed mass changes be explained by changes in the depth of the boundary layer. In the summer, nighttime increases in aerosol mass ranged from 2.7-fold to 81-fold, depending on particle size, while in the winter, the range was narrower, from 2.2-fold to 9.5-fold, supporting the possibility that the presence of particles derived from biomass burning reduced the overall ability of the aerosols to absorb water. Key Points Diurnal cycle of agro-industrial aerosol mass governed by humidity Biomass burning emissions act to suppress particle growth Need to consider diurnal mass cycles in aerosol dry deposition models ©2013. American Geophysical Union. All Rights Reserved.

Ultrasound-assisted extraction of Na and K from swine feed and its application in a digestibility assay: A green analytical procedure

The study is aimed to evaluate the efficiency of ultrasound-assisted extraction (UAE) as a simple strategy focused on sample preparation for metal determination in biological samples. The extraction of sodium and potassium extraction was carried out from swine feed followed by determination of the concentration of these metals by flame atomic emission spectrometry (FAES). The experiment was performed to cover the study of the variables influencing the extraction process and its optimal conditions (sample mass, particle size, acid concentration, sonication time and ultrasound power); the determination of these analytical characteristics and method validation using certified reference material; and the analysis of pre-starter diets. The optimal conditions established conditions were as follows: mass: 100 mg, particle size:<60 μm, acid concentration: 0.10 mol L-1 HCl, sonication time: 50 s and ultrasound power: 102 W. The proposed method (UAE) was applied in digestibility assays of those nutrients present in different piglet pre-starter feeds and their results proved to be compatible with those obtained from mineralized samples (P < 0.05). The ultrasound extraction method was demonstrated to be an excellent alternative for handless sampling and operational costs and the method also has the advantage of does not generating toxic residues that may negatively affect human health and contaminate the environment. © 2013 Elsevier B.V. All rights reserved.